Love of money (LOM) is concerned with the attitude toward money, which can be measured by the LOM scale through affective, behavioral, and cognitive dimensions. Research has observed that monetary attitude was tightly related to reward processing and could affect economic behavior. This study examined how monetary attitude modulated risky behavior and the underlying neural mechanisms of reward processing using event-related potential (ERP) technique. We compared both the risk level and brain responses of a high-level LOM (HLOM) group to a low-level LOM (LLOM) group using a simple gambling task. The behavioral results showed that the HLOM group was more risky than the LLOM group, particularly after loss. The feedback-related negativity (FRN) was measured as the difference wave (gain-related ERP was subtracted from loss-related ERP). The FRN difference wave was larger in the HLOM group than that in the LLOM group. The P3 in the HLOM group was more positive than that in the LLOM group. These results suggest that monetary attitude can modulate both the underlying neural mechanisms and behavioral performance in a reward-related task. The HLOM participants are more sensitive to gain/loss than the LLOM participants.